DE2740884A1 - IMPROVED ELECTROLYTE FOR OPERATING ELECTROCHEMICAL HALOGENID CELLS - Google Patents

Description

Dr. Walter Nielse! ι Patent attorney

Slfluewöfl 43. 2000 H ifPl) ur _: j Femruf. j * 4 "> 5

ECO-CONTROL, INC.
PO box 305
Cambridge, MA Ο2138
United States

Improved electrolyte for operating electrochemical halide cells.

The present invention relates to a method for improving the performance of electrochemical cells, in particular to water-insoluble organic electrolytes which form a complex with halogen and electrochemical in two-phase electrolytes Cells and accumulators, which have halogen as an electrochemically active agent, are used.

Galvanic cells which have an aqueous solution of a zinc or cadmium halide as an electrolyte are known. However, such cells have a relatively high rate of self-discharge, low power and high internal : Resistance on. It is difficult or metallic zinc! Cadmium and elemental halogen in a cell with a, with Regarding the theory, high absorption capacity, to be kept separate as elemental halogen is soluble in the aqueous electrolyte.

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Various methods of preventing migration of elemental halogen to the zinc or cadmium electrode have been described. For example, US Pat. No. 3,352,720 describes the use of a water-insoluble polymeric amine-halogen complex as a replacement for elemental halogen. The cells described in this patent are halogen cells which, however, because of the low stability of the polyhalogens used, not optimal Have power and self-discharge properties.

Another improvement in electrochemical halogen cells is disclosed in US Patent Application 652,780 entitled "Halogen Electrode "dated January 27, 1976. This patent application describes an electrode which has a current collector matrix with extremely stable plastic containing quaternary ammonium, phosphonium or sulfonium sites in the structure. Since the plastic is formed with a large surface area in the presence of a porous current collector matrix, the electrodes can Store halogen atoms in a chemically inactive but in an electrochemically highly active state so that a uniform, Intimate electrical contact between the halogen-rich points of the plastic and the current collector is ensured and one Interaction between the halides in the electrolyte and the quaternary sites is ensured.

US Pat. No. 3,408,232 describes the use of organic solvents to extract bromine from aqueous ones Electrolytes. Although this patent presents a two phase solution to halogen storage, the rate of discharge is I. of the halogen dissolved in the organic phase is insignificant, since I

the organic phase has only low ionic conductivity. j shows. Thus the halogen has to be extracted back into the aqueous phase before a discharge is obtained. This means, that the aqueous electrolyte of these cells must partially surround the two electrodes.

U.S. Patent 3,816,177 describes the use of soluble ones quaternary ammonium halides which are dissolved in the electrolyte together with a water-soluble depolarizer can. If elemental halogen is released into the electrolyte, it combines with the quaternary halide whereby a

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quaternary polyhalide is formed which forms a complex with the depolarizer, so that an insoluble, halogen rich, oil-like complex arises. If an inert electrode made of a material which absorbs the insoluble complex is used, an improved cell performance is obtained because the complex is relatively stable and because the halogen molecules, which are concentrated around the current collector, are available for the electrochemical reaction.

The present invention describes an improvement in electrochemical Halogen cells and particularly describes a number of water-insoluble organic electrolyses which are related can be used with the aqueous electrolytes of the known metal halogen cells of the type described. Through commitment the organic electrolytes of the invention obviate the need to use a depolarizer. Conventional Electrodes are used. In this way, an improved formation of halogen complexes is obtained, thereby reducing the service life of the bearing and the capacity of the cells and accumulators in which they are used is largely improved.

In general, the present invention describes water-insoluble organic electrolytes for complex formation with halogen in connection with a known aqueous electrolyte of the known electrochemical halogen cells. According to the present invention, the organic electrolyte has two components, the first component being an organic solvent which is relatively insoluble in water. The second component used is an organic salt which is highly soluble in the organic solvent and relatively sparingly soluble in an aqueous solution of a metal halide, which forms complexes with halogens which do not crystallize out of the solvent when the halogen is added and which does not react irreversibly with free halogens comes in.
Examples of such solvents are:
Dichloromethane (methylene chloride)
chloroform

Carbon tetrachloride
Dichloroethane

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Trichloroethane, tetrachloroethane, pentachloroethane, Dibromomethane (methylene bromide) bromoform

as well as any solvents which do not react with halogen

enter.

Organic salts which are used according to the present invention can include e.g.

Ammonium salts

R ia

R, - N d,

! R.
, a

R -! R, N - R, e i d, b I R

n +

-R nX

Pyridinium salts

R,

n +

n * h

nX

Sulfonium salts

R e

n + -R.

nX

Phosphonium salts

x "

n +

in which the substituents R are independently selected from hydrogen, aliphatic radicals, O-alkyl radicals, functional aliphatic or O-alkyl radicals, aryl radicals, and / or functional aryl radicals, where the functional groups of these aliphatic or aryl radicals are e.g. amides, homocyclic carbon compounds, carboxylates, halides, hydroxides, ethers, esters, nitriles, phosphonates, siloxanes, Sulphonates, sulphones, and sultones may include and the counter ions:

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(X) such cations are selected from F, Cl, Br and I.

The present invention thus describes an electrolyte which enters into a complex formation with halogen, which in a aqueous metal halide solution is insoluble and which are used in cells and accumulators of the type described can. Complex formation with elemental halogen significantly improves the performance of electrochemical halogen systems obtain.

The electrolytes described according to the present invention can be used in zinc or cadmium halide cells to form complexes with and storage of halogens can be used effectively. The electrolytes of the present invention have with reference to polymeric amine halogen complexes and systems of quaternary ammonium polyhalide and depolarizer have various advantages such as an extension of the shelf life and a lowering self-discharge.

The electrolytes of the present invention, together with halogen, form complexes which are in the form of liquid phases in water and are insoluble in aqueous metal halide solution and are used to react the halogen to the halogen cells or accumulators Provide.

The electrolytes of the invention form complexes with halogen which are conductive liquids of which the halogen is one rapid electrochemical reaction at the electrode of a halogen cell or a halogen accumulator in contact with it Electrolytes can enter.

The complexes of the invention formed with halogen are liquids which can be transported by pumps and stored for an indefinite period of time and which can be used in a regenerative fuel cell or a regenerative accumulator the carbon electrode ■ or plastics, which of uncomplexed ι elemental halogen quickly attacked, not attacked.

'For a better understanding of the invention, reference is made to the following description of examples and to the two

: lying figures where:

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Figure 1 is a cross-sectional view of a cell in which the complexing electrolytes of the invention can be used;

FIG. 2 shows a graph of the ionic conductivities;

FIG. 3 shows a schematic representation of a regenerative fuel cell in which an electrolyte of the present invention circulates; and

FIG. 4 shows a cross section of a storage battery in which the complex-forming electrolytes of the present invention can be used,
represent.

For a better understanding of the following description, individual terms are explained. For example, the term means "Zinc electrode" or "bromide electrode" does not mean that these electrodes only consist of these materials. These expressions describe only the electrochemically reactive component of the electrode. The metal and halogen electrodes of the cells in which the electrolytes of the invention are electrically conductive, porous and non-corrosive. Most preferred carbon is used. Zinc and cadmium are galvanized onto the surface of the carbon and thus form the metal electrode.

Although reference is made in the description to the counter electrode and a metal electrode is evident that the present invention can also be used in other cells which have more than one Have a pair of electrodes, and can be used in accumulators, which consist of two or more cells. j

Since, from an electrochemical point of view, cadmium and zinc are similar: the zinc of the electrode and the electrolyte is of course through!

I Replaceable cadmium. Although reference in the following description!

is taken, on bromine, it is clear to the experts that:

ι chlorine, iodine or a mixture of bromine, chlorine or iodine used j

can be.

When the well-known zinc-bromine cell is discharged, the

received the following response:

at the cathode Br ₂ + 2e * 2Br

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at the anode Zn >> · Zn + 2e

When the cell is charged, the reverse reactions are obtained:

at the cathode 2Br ~ - * · Br_ + 2e ~

++ - 0 at the anode Zn + 2e - ♦ Zn

Zinc bromide from the electrolytes is thus consumed when the cell is charged and is formed when the cell is discharged. To a To ensure that the cell works properly, Br, which is required at the cathode when the cell is discharged, is stored will. Since Br_ is soluble in aqueous metal halide solutions, migration through the aqueous electrolyte must lead to the Anode, at which Br- would react with metallic zinc, can be prevented. This is done by installing a porous, conductive, preferably carbon, die as described in US Pat. No. 3,816,177 entitled "Secondary Cells and accumulators described, and an electrolyte of the invention obtained. It should be noted here that the The organic phase of the two-phase electrolyte does not have to have a higher density with respect to the aqueous phase. if the If the density of the organic phase is greater than that of the aqueous phase, the bromide electrode 16 should be attached to the bottom of the cell on which it is covered by the organic phase of the two-phase electrolyte (Figure 1). By installing the bromide electrode at the bottom of the cell and by using an organic solvent which is heavier or denser than the aqueous one Phase, the organic phase of the two-phase electrolyte is absorbed in the porous electrode 16 and that during charging ' The halogen formed forms a complex with the salt dissolved in the organic phase, so that it is not aerated ι phase of the electrolyte can dissolve. ;

ίThe use of halogenated solvents to store Bromine in secondary cells was described in US Pat. No. 870,973. The use of solid quaternary ammonium perhalogen salts for Storage of bromine in secondary cells is described in US Patent 2,566,114. However, both methods have the disadvantage

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that the conductivity of the halogenated phase is insufficient so that only a low discharge rate is obtained. This problem was addressed by using a water soluble organic solvent according to US Pat. No. 3,816,177. This solvent made the halogen complex liquid and thus kept conductive. In contrast, the present invention describes the use of a water-insoluble one organic solvent with an addition of an organic salt to complex with the halogen and to increase the Conductivity of the insoluble organic solvent in the Electrolytes. The organic phase of the two-phase electrolyte of the invention forms a multi-component layer which the Separates halogen from the aqueous metal halide solutions which form the aqueous phase.

As already stated above, one of the components consists of the organic phase of the two-phase electrolyte, which complexes with halogen, from an organic solvent that is relatively insoluble in water. Solvents which, for example, as organic Phase according to the present invention can be used include:

Dichloromethane (methylene chloride)

chloroform

Carbon tetrachloride

Dichloroethane

Trichloroethane

Tetrachloroethane

Pentachloroethane

Dibromomethane (methylene bromide)

Bromoform

as well as any water-immiscible solvents which,

do not react with bromine. \

The second component, the organic phase of the two-phase electrolyte, which forms a complex with halogen an organic salt used, which is readily soluble in the organic solvent, in an aqueous metal halide solution is insoluble, which forms complexes with halogens

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-Jf-

Halogen additive does not crystallize out of the solution and which cannot react irreversibly with free halogen.

Organic salts which can be used in the present invention include e.g.

Ammonium salts

R, - N -

Pyridinium salts

Sulfonium salts

I S

χ -

R e

R -

n +

n +

^R h

-R-S-

n +

-R

nX

^R d " _ R. C. U i ^a Phosphonium ¹ D - Ό salts I. R.

R -

- ^R d- ^p -v

n +

; wherein the various substituents R independently ', can be selected from Viasserstoff, aliphatic radicals, O-alkyl radicals, aliphatic or O-alkyl radicals, aryl radicals and / or functional tional aryl radicals, i functional tional wherein the functional tional groups of these aliphatic and aryl' radicals are selected can from the amides, homocyclic

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/ is

Carbon compounds, carboxylates, halides, hydroxides, Ethers, esters, nitriles, phosphonates, siloxates, sulfonates, sulfones and sultones and the counterions (X) can be selected from the group consisting of F, Cl, Br and I.

The following can be listed as examples of such salts: pentyl tripropyl ammonium bromide, methyl triethylammonium bromide, Diethyl methyl propyl ammonium bromide, butyl tripropylammonium bromide, Ethyl tributyl ammonium bromide, tetrapentylammonium bromide, Ethyl tripropyl ammonium bromide, butyl triethylammonium bromide, Propyl triethyl ammonium bromide.

The synthesis of these cations becomes pure by adding alkyl halide to divalent (S) or trivalent (N or P) bases or diluted form in a number of known solvents.

Example A:

In a 250 ml round bottom flask, 14.3 g of tri-n-propylamine in 75 ml of a 1: 9 methanol-nitromethane mixture with 16 g of ethyl bromide treated and heated to 65 ° C for 36 hours under a water-cooled cooling tube. The methanol-nitromethane The mixture was evaporated under reduced pressure and the residue was suspended in a 1: 9 acetone-hexane mixture to obtain complete crystallization. After freezing to a temperature of 0-4 for 2 hours, it became crystalline The product was separated off and dried, 23.5 g (94%) of coarse, white needles having a melting point of 29O-291 ° C. according to FIG following response were obtained:

CH CH Br
(CH ₃ CH ₂ CH ₂ J ₃ N > (CH ₃ CH ₂ CH ₂ ) ₃ N ^ ^CH 2 ^CH 3 ^Br (ECO-I)

Example B.

In a 250 ml round bottom flask, 10.5 g of triethylamine in 50 ml of nitromethane were treated with 1-bromobutane. The round bottom flask was sealed and kept at room temperature for 72 hours. The nitromethane was evaporated off under reduced pressure, giving a solid residue which was recrystallized from an acetone-hexane mixture. 19.5 g (92%) of a white crystalline quaternary salt ^ mi_t_ a melting point of 2o8-211

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C were obtained. The reaction can be represented as follows:

CH CH CH CH Br _φ

(CH ₃ CH ₂ ) ₃ N - - - --- »(CH ₃ CH ₂ ) ₃ N CH ₂ CH ₂ CH ₂ CH ₃ Br

The amount of complex-forming salts (with halogen) which is dissolved in the organic phase is both for the conductivity as well as for the bromine separation coefficient in relation to the aqueous electrolyte phase. The solubilities of a number Quaternary ammonium bromides in methylene chloride are listed in Table 1.

Table 1
Solubilities of quaternary ammonium bromides (5 mM) in methylene chloride

at 25 ° C g MeCl ₂ g MeCl ₂ HCB * Quaternary Anion Br
0.939 Anion Br, <S
0.939 14th Cation (5 mM)
Pr ₃ PenTlr 0.962 0.962 24 HeX ₄ N 1,000 2,325 16 4 * ~, 1.036
1.167
1.275
1.351 1.036
1.167
1.275
1.351 7th
8th
13th
14th Et-, MeN *
Et ₂ MePrN
BuPr ₃ N ^
Bu, EtN® 1,600 1,600 20th Φ
Pent ₄ N 1,600 1,600 11 EtPr ₃ N 1,600 1,600 10 BuEt ₃ Ν ^Φ 1,600 1,600 9 Et ₃ PrN 1,600 1,600 28 Hept.N® 2.197
2,423
5.388 - 12th
15th
6th Pr ₄ N *
CH ₂ EtMeN ⁶
Et ₂ Me ₃ N * 12,863 - 8th 17,542 - 7th EtMe ₃ IPrN ^

* HCB = hydrogen-bearing carbons in the cation.

Bu = butyl

Ch = cyclohexyl

Et = Aethy1

Hept = heptyl

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Hex = hexyl Me = methyl Pent = pentyl iPr = isopropyl Pr = propyl

Since the organic phase must remain liquid, the ammonium polyhalides must be soluble at this stage. The only cation described above in which the polybromide is less soluble as the bromide is the tetrabutylammonium cation. Ionic conductivities which were listed in Table 2 or in Figure 2 prove that the conductivity is inversely proportional to the size of the cation, i.e. the smaller the cation, the greater the conductivity.

Table 2 Quaternary mM quaternary ammonium in 1.60 g MeCl- Conductivity Si -cm Conductivity: 5 cation Conductivity Jl-cm Anion Br, ^ HCB * Hept.N. Anion Br 635 Hex.N *
4 f. 1600 277 28 ft)
Pent.N 1000 107 24 Bu ₄ N ^ 535 Crystalline 20th Bu ₃ EtN * 325 88 16 Pr ₃ Pe _n tN ⁴ * 255 73 14th BuPr ₃ N 165 63 14th EtPr ₃ N ⁶ ' 162 69 13th BuEt ₃ N * 131 43 11 Et ₃ PrN ⁸ * 83 33 10 Et ₂ MePrN * ¹ 86 25th 9 Et ₃ MeN * 60 20th 8th = Hydrogen 46 in the cation 7th Butyl carrying carbons * HCB Ethyl Bu = = Heptyl Et = Hexyl Hept methyl Hex = = Pentyl Me = Propyl Pent Pr =

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+ Conductivity determined at 1 KC at 25 C between the tips of two conical carbon electrodes and with reference to IN KOH Standardized solution.

The higher ionic conductivity of polybromide anions is probably due to a transition diffusion (I. Ruff and V.J. Friedrich, J. Phys. Chem. 76, 2957 (1972)). The separation of the bromine between the two electrolyte phases was determined by titration determined and is given in Table 3.

Table 3

Quaternary ammonium bromide solvent % Br in organic 33.2 (3.28 mM) (0.795 ml) phase 91.4 no CHpCl 92.2 [EtPr ₃ N] ⁺ Br " CH ₂ Cl ₂ 90.9 [EtPr ₃ N] ⁺ Br " CH ₃ Br ₂ 87.7 [Et ₃ NCH ₂ CH ₂ OCH ₂ CH ₃ ] ⁺ Br " CH ₂ Cl ₂ [BuEt ₂ NCH ₂ CH ₂ OHl ⁺ Br " CH ₂ Cl ₂

The bromine used was 0.504 ml per test Br_. 5 ml (2M) aqueous zinc bromide were used. Each test solution was vigorously stirred for 45 minutes at 25 ° C before the Bromine content was determined by titration.

Figure 1 illustrates a cell 10 with a two-phase electrolyte of the present invention in which the organic phase is denser than the aqueous phase. The cell comprises a housing 12, a pair of graphite electrodes 14, 16, a graphite fleece mass 18 and a porous polymer separating plate 20. The graphite electrode 16 represents the bromine electrode, the electrode 14 the zinc electrode Electrical leads (not shown) can be attached to electrode 14 with clips. Through the case 12 leads a line to the electrode 16. A seal is in the housing 12 at the point at which the line enters the housing penetrates provided. The electrodes 14, 16 have a porosity of 26%. A suitable graphite fleece can be obtained commercially from the Union Carbide Corporation (VWF grade) and a suitable cutting wheel from W.R. Grace Inc. under the brand name DARAMIC. The cell electrolyte has inorganic salts such as

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Zinc halide or cadmium halide and can contain between 0-30% of various additives to improve metal plating exhibit. The cell housing 12 is provided with non-wettable porous plugs 13 formed by them on the zinc electrode 14 Hydrogen gases can escape. The heavy organic phase during charging and discharging is caused by gravitational forces of the cell held in the graphite fleece mass 18. During the charging and discharging of the cell, the lighter becomes watery Phase held on the zinc electrode 14 by gravitational forces.

FIG. 3 shows a cell 21 in which a two-phase electrolyte is circulated. The cell 21 comprises a housing 22, a pair of graphite electrodes 21, 24, a graphite fleece mass 25 and a porous polymeric separating plate 26. The system for storing the halogen complex phase 27 and for supplying fresh electrolyte comprises pumps 28, 28 ', a container for electrolyte storage 29, a container for storing the halogen complex phase 30 and valves 31 and 32. When charging, the halogen complex phase 27 is formed in the fleece 25 from the organic phase of the electrolyte. The halogen complex phase 27 obtained is passed into the container 30 from which it can be pumped back into the fleece 25 for discharging the cell or for a controlled supply of halogen into the electrolyte. When the cell is charged, the metal is electroplated onto the electrode 23, the quality of the electroplating depending on the throughput rate. The organic phase of the electrolyte 33 is stored in a container 34. With the aid of valves 35 and 36, organic electrolyte 33 can be stored or released. The aqueous electrolyte phase of the cell comprises inorganic salts such as zinc or cadmium halide as well as between 0 and 30% of one or more additives to improve the galvanization.

It will be apparent to those skilled in the art that the complex 27 can be used to operate other cells. In addition to zinc and cadmium cells, the complexes can also be used in other electrochemical halogen cells, which have, for example, titanium, iron, chromium, hydrogen or organic redox phases as anode.

To demonstrate the effect of the compound of the present invention, a cell with a circulating two-phase electrolyte,

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which was described above, and ECO-I contained at a current

2 density between about 108 and 646 A / m for 1 to 3 hours charged. The cell was subjected to a series of tests at a constant discharge current for various current densities it was found that it ensured a current efficiency of 50-80% and an energy efficiency of 40-60%. Without the two-phase electrolyte In the present invention, no halogen complex 27 was formed and the bromine which was in the electrolyte reacted with the zinc electroplating of the electrode 25 with a current and energy yield of less than 5% became.

FIG. 4 shows a bipolar, multi-cell accumulator

3 7 with a two-phase electrolyte of the present invention. This accumulator comprises a watertight glass housing 39, a pair of graphite plates as current collectors 41, 43 to which electric wires (not shown) are attached. The plate 43 serves as a metal electrode, the plate 41 as a halogen electrode. Between the current collectors 41, 43 there are graphite fleece masses

4 5 arranged as a counter electrode in conjunction with a bipolar electrode, a porous polymeric separator plate 47 (DARAMIC, approximately 0.32 cm thick), and a bipolar electrode 49 (conductive plastic film from Conductive Polymer Corporation, Marblehead, Massachusetts, approximately 0 , 05 cm thick) acts. As can be seen from the figure, the separating plate 47 and the bipolar electrode 49 are arranged between the graphite fleece mass 45. The cell housing is provided with a non-wettable, porous plug 51 so that hydrogen gas, which is formed at the zinc electrodes 43 and 49, can escape. \ The number of battery cells can of course be increased or decreased as required.

If the organic phase is denser than the aqueous phase, the heavier organic phase becomes due to gravitational forces held in the graphite fleece mass 45 during the charging and discharging of the cell. The lighter, aqueous phase is through Gravitational forces are held on the zinc electrodes 43 and 49 during the charging and discharging of the cell. It is clear that the surfaces of the bipolar electrode, which are the metal

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-yr-

Electrode 43 are facing, act as a halide electrode, whereas the surfaces that face the halide electrode 41 are facing to act as metal electrodes.

By adjusting the cells used, organic phases can also be used which are lighter than the aqueous phase. If a cell with circulating electrolyte is used and the cell is operated in a vertical position, the density of the organic phase is unimportant. In these cells, the organic phase flows through the porous graphite fleece mass 18th

The present invention thus describes a new electrolyte composition for electrochemical halogen cells or accumulators with significantly improved performance and current yield.

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Claims (8)

Dr. Walter Nielsch Sirius.veg 4.J ₁ 2üOG H'i.TtiJijr-j ·.;.; i Far:, call 304 l>, i Claims fli electrochemical halogen cell consisting of a housing, a porous, conductive halide electrode, a metal electrode, wherein the metal is selected from the group consisting of zinc and cadmium, an aqueous electrolyte which has an inorganic salt of the formula MX, where M is selected from the group consisting of cadmium and zinc, and X is selected from the group consisting of bromide, Chloride, iodine or a mixture of these halide ions, and an organic electrolyte, characterized in that the organic electrolyte surrounds the halide electrode and consists of two components, the first component being in water is relatively insoluble organic solvent and the second component is an organic salt which is present in the organic Solvent is highly soluble and is relatively insoluble in the aqueous metal halide electrolyte, forms complexes with halogen which do not crystallize out of the solution when halogen is added and which do not react irreversibly with free halogens comes in. - 2- 2740834 2. Electrochemical halogen cell according to claim 1, characterized / that the organic solvent is a solvent selected from the group consisting of dichloromethane, chloroform, Carbon tetrachloride, dichloroethane, trichloroethane, tetrachloroethane, Pentachloroethane, dibromomethane and bromoform are used will. 3. Electrochemical halogen cell according to one of claims 1 to 2, characterized in that the organic salt is selected is made up of the group consisting of: Ammonium salt of the formula R. Pyridinium salt of
formula i ^a N Rc ^R b R e R, - N - R, d b R - n + -R _f nX n + nX -R, Sulfonium salt of the formula i ^R d - x " R - R ι ^a S - n + -R, nX d t R ^R b n + in which the various substituents R are selected independently of one another from hydrogen, aliphatic radicals, O-alkyl radicals, functional aliphatic or O-alkyl radicals, Aryl radicals and / or functional aryl radicals, j where the functional groups of the aliphatic or aryl 809811/0964 .3-2740834 radicals can be selected from amides, homocyclic carbon compounds, carboxylates, halides, hydroxyls, Ethers, esters, nitriles, phosphonates, siloxanes, sulfonates, sulfones and sultones, and the counter electrodes (X) are selected are made from F, Cl, Br and I. 4. Electrochemical halogen cell according to one of claims 1-3, characterized in that the salt is selected from the group: pentyl tripropyl ammonium bromide, methyl triethylammonium bromide, Diethy1-methy1-propy1-ammonium bromide, Butyl tripropyl ammonium bromide, Aethy1-tributy1-ammonium bromide, Tetrapentyl ammonium bromide, ethyl tripropy1 ammonium bromide, butyl triethyl ammonium bromide, propyl triethyl ammonium bromide. 5. Process for improving the power and current yield electrochemical halogen cells according to claim 1, wherein halogen is selected from the group consisting of bromine, Chlorine, iodine and mixtures thereof in which an electrochemically active agent is electrochemically applied to the halide electrode reacts with the system having an electrolyte consisting of an aqueous metal halide solution, characterized in that that the halide electrode of the system is surrounded by an organic two-component electrolyte, the first Component is an organic solvent which is relatively insoluble in water and the second component is an organic one Salt represents which is highly soluble in the organic solvent and in the aqueous metal halide electrolyte is relatively insoluble, forms complexes with halogen which do not crystallize out of the solvent when halogen is added and which does not react irreversibly with free halogens. 6. The method according to claim 5, characterized in that the organic solvent is selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride ,; Dichloroethane, trichloroethane, tetrachloroethane, fentachloroethane, ■ Dibromomethane and bromoform. ! 7. The method according to any one of claims 5-6, characterized in that that as an organic salt a salt selected from the 80981 1/0964 Group consisting of Ammonium salt of the formula R, ^d ι ^ε N Re n + Pyridinium salt of formula Sulfonium salt of the formula R N e ι ι ^£ R - R e n + -J η -v ^s -v R.
. ^a n + -R _d nX η + in which the various substituents R are independently selected from hydrogen, aliphatic
Radicals, O-alkyl radicals, functional aliphatic or O-alkyl radicals, aryl radicals and / or functional aryl radicals, the functional groups being the aliphatic
or aryl radicals are selected from amides, homocyclic carbon compounds, carboxylates, halides, hydroxyls, ethers, esters, nitriles, phosphonates, siloxanes, sulfonates, sulfones and sultones, and the counter electrodes (X) selected from F, Cl, Br and I are used will. 80981 1/0964 8. The method according to any one of claims 5 to 7, characterized in that a salt is selected as the organic salt is from the group: Pentyl-tripropyl-anunonium-bromide, Methyl triethyl ammonium bromide, diethyl methyl propyl ammonium bromide, Butyl tripropyl anunonium bromide, ethyl tributyl ammonium bromide, Tetrapentyl ammonium bromide, ethyl tripropyl ammonium bromide, butyl triethyl anunonium bromide, propyl triethyl ammonium bromide. 809811/0964